Polymerizable polyallyl ester composition



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Patented June 8, 1954 POLYMERIZABLE POLYALLYL ESTER COMPOSITION Thomas F. Anderson, Huntsville, Ala., assignor, by mesne assignments, to Allied Chemical & Dye Corporation, New York, N. Y., a corporation of New York No Drawing. Application May 26, 1952, Serial No. 290,088

The invention relates to a polymerizable polyallyl ester composition which upon polymerization has improved water resistance and electrical properties.

In a filled polyallyl ester composition, such as a molding composition, the filler is an extremely important ingredient. It is difiicult to prepare a filled polyallyl ester composition that has sufficient viscosity to permit it to be molded in commercial equipment. Filled polyallyl ester compositions tend to be too fluid to be handled in such equipment; filled compositions that are too fluid have a tendency to squirt out of the mold. Various precautions must be taken in the preparation of a filled polyallyl ester composition in order to avoid excessive fluidity. Among the factors that must be regulated carefully to provide satisfactory molding properties are the nature and the amount of the filler.

The filler in such a composition also has a very important effect upon the strength of articles molded from the composition and upon the resistance of such articles to moisture.

Because of the diificulty of preparing a filled polyallyl ester composition which has satisfactory moldability and produces molded articles of satisfactory strength, the selection of a satisfactory filler for such a composition is a diflicult problem. Certain fillers which tend to improve the water resistance of the molded articles also tend to cause serious impairment of the strength of such articles. Polyallyl ester compositions are of great potential value for the production of water resistant articles, but this potential value has not been realized heretofore because the fillers heretofore used in such compositions have prevented the attainment of high water resistance in the molded articles.

The principal object of the invention is the production of a filled polyallyl ester composition of satisfactory moldability that produces molded articles having not only satisfactory strength but also excellent water resistance and electrical properties. More specific objects and advantages are apparent from the description, which illustrates and discloses but is not intended to limit the invention.

The present invention is based upon the discovery that molded articles having very satisfactory strength and having excellent water resistance and electrical properties can be obtained from a composition which has satisfactory moldability and comprises (a), as a binder, a polymerizable polyallyl ester, and (b), as a filler, kaolin that has been dehydrated by calcining at 600-1200 C.

The unique and outstanding results obtained in the practice of the present invention have been demonstrated as follows:

'7 Claims. (Cl. 260-173) A molding composition of the invention was prepared as follows:

A solution of a partially polymerized polyallyl ester (2800 grams consisting of 50 per cent by weight of acetone solvent, and 50 per cent by weight of diallyl phthalate of which 95 per cent was in the form of a soft, solid, fusible polymer melting in the range from 210 to 220 degrees F.) was mixed in a Hobart dough mixer with a catalyst (56 grams of t-butyl perbenzoate), a filler (2600 grams of dehydrated kaolin) and a lubricant (80 grams of zinc stearate). The mixing was continued until a homogeneous material was obtained, which material was then dried at 140 degrees F. for three hours to remove the excess of acetone solvent. The material was then milled on differential rolls for about ten minutes. The resulting sheet was cooled and was then granulated in a high speed cutter.

For the sake of comparison, control compositions were prepared as follows:

Control composition 1 was prepared by the procedure described above for the preparation of a composition of the invention (hereinafter referred to as composition A), except that ordinary kaolin was used in place of the dehydrated kaolin.

Controlcomposition 2 was prepared by the procedure described for composition A except that the filler consisted of cellulose flock (1200 grams) and the proportions of the other ingredients were as follows: 3600 grams of the solution of partially polymerized diallyl phthalate; '72 grams of t-butyl perbenzoate; and 60 grams of zinc stearate.

Control composition 3 was prepared by the procedure described for composition A except that the filler consisted of chrysotile fibers (2480 grams) and the proportions of the other ingredients were as follows: 3040 grams of the solution of partially polymerized diallyl phthalate; 60.8 grams of t-butyl perbenzoate; and 80 grams of zinc stearate.

The composition of the invention (A) and the control compositions were molded (under one to four tons of pressure per square inch of projected area in a mold heated with steam at lbs. gauge pressure) into disks which were cured for approximately two to five minutes at 310 degrees F. and were then tested by the following procedures:

The disks were immersed in water, and the water absorption was measured as the gain in weight (in grams) during immersion. (Water resistance varies with the amount of moisture that an article is capable of absorbing" because the degree of deterioration upon exposure to moisture varies with the amount of moisture absorbed.) In Table 1 below, the water absorption is given for tests in which test pieces made from molding composition A (column 2) and 3 control molding compositions 1, 2 and 3 (columns 3, 4 and 5) were immersed in boiling water for one hour (line 1), and in cold water for 24 hours (line 2) or 48 hours (line 3) or '7 days (line 4) The electrical properties of disks inch thick and 4 inches in diameter) molded from the compositions are also shown in Table 1 below (lines 5, 6, '1 and 8).

Insulation resistance is one of the most important qualifications of a synthetic resin for use in electrical applications. Insulation resistance may be defined as the resistance offered to the flow of a current when a voltage is impressed between two electrodes embedded in a hardened composition at a standard distance. In an accelerated test used to determine the retention of insulation resistance by compositions embodying the invention, the polymerized compositions are exposed to high relative humidities and high temperatures for prolonged periods of time to promote the breakdown of their insulation resistance. The insulation resistance is then determined by measuring the resistance (in megohms) offered to the flow of a current when a voltage is impressed between two electrodes so embedded in a molded article that there is a distance of 1 inches between the centers of the electrodes. (The initial insulation resistance of each sample is over one million megohms.) The results of the insulation resistance tests after exposure of articles molded from composition A and from the control compositions to a temperature of 160 degrees F. and a relative humidity of 95 per cent for various lengths of time are given in Table 1 below (line 9). (The erratic resuits are due largely to the extreme diificulty of measuring high resistance under conditions prevailing in the humidity test chamber.)

Table 1 also includes the results of strength tests on bars (6" x V x A") molded from composition A and from the control compositions. The strength tests employed are standard tests for plastic materials and are considered to be capable of showing generally the strength characteristics that are important in industrial plastic materials. The flexural and compressive strengths (lines 10 and 11) and the flexural moduli (line 12) of the molded bars are shown in Table 1.

TABLE 1 Composition A Oontroll Control 2 Control3 1. Boiling water absorption, 1 hr 010 .030 O 025 2. Cold water absorption, 24 hrs 010 .010 055 010 3. Cold water absorption, 48 hrs 015 .015 (l8 M5 4. Cold water absorption, 7 days .020 040 175 .035

5. Dielectric constant,

60 cycles 4. 2 4. 64 4. 64 114i 6. Dielectric constant,

10 cycles 3. 6 4. 24 3. 84 4. 13

7 Power Factor, 60

cycles 022 Us! .127 107 8. Power Factor, 10'

cycles 0126 O61 045 064 9. Insulation Resistance 151 82 12 12 9 155 30 3 ys. 155 28 7 l0. Flexural (p. s. i.). 3, 940 6,690 7, 380 11. Compressive (p. s, 1.)- 22, 500 15, 200 25, 100 22, 800

12. w g hm 1. 3a 1.32 .94 1. 52

As the results in Table 1 indicate, the resistance to hydrolysis of articles molded from a polymerizable polyallyl ester composition of the invention which comprises dehydrated clay as a filler is greater than the resistance to hydrolysis of articles molded from a similar composition which, however, comprises ordinary kaolin or cellulose or asbestos as a filler. In fact, the resistance to hydrolysis of articles molded from a composition of the invention is so superior that such article show much better retention of electrical properties after exposure to high humidity than articles molded from a similar composition which does not comprise dehydrated clay as a filler. At the same time, the use of dehydrated clay as a filler in a polymerizable polyallyl ester composition produces molded articles of very satisfactory strength, as is evident from the strength test results in Table 1.

Binder The binder in a composition of the invention comprises a polymerizable polyallyl ester. Such a substance may be an ester or mixed ester of two alcohol molecules, each consisting of a molecule of allyl, methallyl or beta-chloroallyl alcohol, with a molecule of any of the dibasic acids listed in Table 2 below.

TABLE 2 O Maleicacid HC -OH u 0 HO-2OE O Chloromaleic acid l. ClC-%OH 1 0 HC-% JOH O Brornomaleic acid Br-C% 3OH O HC -QI-OH 0 Fumarioacid H0P3(H 0 Hu- OH O Chlorofumeric acid HO( 7("CI O H(./(%OH Bromofumaric acid HO(3(Br HL1- OH O Mesaconic acid HO--P-CHa O Hb(%-OH Citraconicacid CH3C 3OI-I 0 H JOH ll Benzene dicarboxylic acid" HOC TABLE 2 Continued 0 CH2 0 Itaconic acid H0-( CH2g-OH O Carbonic acid HO- OH O O Oxalic acid HO( ]OH O Malonic acid HO (LJ OHQ ICIOH' O O Succinicacid H (CH2)z( -OH O O Glutaric acid HO( (CH );-C )-OH 0 0 Adipic acid HO(%(CH2)4 OH O Pimelic acid HO( %(CH)5( %OH O O Suberic acid HO-( J(OH2)a( JOH O O Azelaic acid HO% J-(CHz)1-K%OH O O Sebacicacid HO -(CHflr-OH O 0 11 ll Biphenyldicarboxylic acid. HO-C-(C )COH I Naphthalene dicarboxylic HO-C( )COH acid u i h e dicarbox lic X33??? HOC(CtH1n)OOH ll (13H: 11 Pyrotartaric acid H -C-CH-CHz-C-OH OH Phenyl phosphonic acid OP\ Benzene dicarboxylic'acid in the foregoing table includes o-,m-, and p-phthalic acid. Similarly, the enclosure of the biphenyl ring and the naphthalene ring in parentheses in the above table is intended to indicate that any of the various position isomers may be used. In the case of cyclohexane dicarboxylic acid, any of the various position isomers may be used either in cis or in trans relationship.

The polymerizable polyallyl ester may also be an ester or mixed ester of a molecule of a tribasic or other polybasic organic or inorganic acid with three or more allyl, methallyl or beta-chloroallyl alcohol molecules. Such substances include triallyl tricarballylate, triallyl aconitate, triallyl citrate, triallyl phosphate, trimethallyl phosphate, triallyl cyanurate, and tetrallyl silicate.

The polymerizable polyallyl ester may also be an ester or mixed ester of (a) a substance having the general formula RO-DOH in which R is allyl, methallyl, or beta-chloroallyl and D is the divalent acid radical of any of the dibasic acids listed in Table 2 with (b) a substance having the attached in any of the dihydroxy compounds listed in Table 3 below.

TABLE 3 Ethylene glycol HOCH2CH2OH OH Propylene glycol i. OHa( JHCHz -0H OH l,2-butylene glycol HOOH2( JHOHzCH3 O H O H 2,3-b utylene glycol CH3 H( HCH3 K Tti-methylene glycol H0(CH2)3-OH Tetra-methylene glycol. HO (CH2)4 0H Penta-methylene glycol H O( CH2) 5-0 H Hem-methylene glycoluw H O-( CH2) e-OH Heme-methylene glycoLm HO( 0 H2) 1-0 H Octa-mcthylene glycol. HO( CH1) s--O H Diethylene glycol", HO-OHz-OHz-O-CHz-C'Hq-OH Triethylenc glycol H0-(OHrCHrO)2-CH2-CHz-OH 'Ictraethylene glycol H O( CHz-CHrO)a-OH2-CHz-OH 0-, mor p-dihydroxy honzeuc.

Such a polyallyl ester thus has the general formula or R-ODO-EO-D-OR. Substances having the formula include the diallyl ester of lacto-carbonate and the diallyl ester of hydroxyaceto-carbonate. Such polyallyl esters may be prepared by reacting -(l) one molecule of an ester of an allyl alcohol (i. e., allyl alcohol, methallyl alcohol or beta-chloroallyl alcohol) with a mono-basic hydroxy-substituted, chloro-substituted or bronco-substituted acid, such as glycolic acid, chloracetic acid, lactic acid, alpha-bromo propionic acid or hydroxy benzoic acid, (e. g., allyl lactate) with (2) one molecule of a half ester of one of the dibasic acids listed in Table 2 with an allyl alcohol.

Polyallyl esters having the general formula R O-DOE-O-DO-R include: diallyl ethylene glycol dioxalate, diallyl ethylene glycol dicarbonate, diallyl diethylene glycol dicarbonate, diallyl trimethylene glycol dicarbonate, diallyl ethylene glycol disuccinate, diallyl ethylene glycol diadipate, diallyl diethylene glycol dimaleate, climethallyl diethylene glycol dicarbonate, diallyl diethylene glycol dimalonate, 2-(oxycarballyloxy) ethyl ethyl fumarate and Z-(oXycarbomethallyloxy) ethyl methyl furnarate.

The polyallyl ester may also consist of an ester of a molecule of any of the dibasic acids listed in Table 2 with two similar molecules (or a mixed ester of a molecule of such a dibasic acid'with two dissimilar molecules) each of which is an ester of glycolic, lactic or mor p-hydroxy benzoic acid with an ally] alcohol. Such a polyallyl ester has the general formula 0 H g R-O-C-B-O-DOB ()R An amino acid such as glycine may be used in place of lactic, glycolic or 0-, mcr p-hydroxy benzoic acid, so that the general formula is then Such polyallyl esters include: carbonyl bis(methallyl lactate), carbonyl bis(allyl lactate), maleyl bis(allyl lactate), fumaryl bis(allyl lactate), succinyl bis(allyl lactate), adipyl bis allyl lactate), sebacyl bis(allyl lactate), phthalyl bis allyl lactate), fumaryl bis(allyl glycolate) carbonyl bis- (allyl glycolate) carbonyl bis(allyl salicylate) and oxalyl bis allyl glycinate).

The polyallyl ester may also consist of an ether of two similar or dissimilar molecules each consisting of an ester of glycolic, lactic or 0-, inor p-hydroxy benzoic acid with an allyl alcohol. Such a substance has the general formula Such substances include the esters of an allyl alcohol with diglycolic acid, with diethyl ether alpha, alpha-dicarboxylic acid, or with any diphenyl ether dicarboxylic acid in which each of the benzene rings has one carboxyl group attached to it. in the preparation of such a compound, an ether or" two hydroxy-substituted acid molecules may first he prepared by reacting the sodium derivatives of glycolic, lactic or any hydroxy-benzoic acid with chloracetic or alphachloropropionic acid in accordance with the usual procedure for preparing others. The product may then be esterified with an allyl alcohol.

The polyallyl ester may also consist of an ether of a molecule of ethylene glycol, propylene glycol, 1,2-butylene glycol, 2,3-butylene glycol or 0-, mor p-dihydroxy benzene with two similar or dissimilar molecules each consisting of an ester of glycolic, lactic or o, mor p-hydroxy benzoic acid with an allyl alcohol. Such a substance has the general formula 0 o H II o o uch a suestance may be prepared by reacting one molecule of a sodium derivative of ethylene, propylene or a butylene glycol or of a dihydroxy benzene with two molecules of an ester of chloracetic acid or alpha-chloropropionic acid with an allyl alcohol, in accordance with the usual procedure for preparing others.

The polyallyl ester may also consist of an ester of a molecule of silicic acid with four molecules of an ester of glycolic or lactic acid with an allyl 8 in which b is methylene or me hyl methylene and R is allyl, methallyl or beta-chloroallyl. Such compounds include te raiallyl glycolate) silicate and tetra(a1lyl lactate) silicate.

The diallyl esters, particularly diallyl phthalate, are preferred in the practice of the invention.

It is most desirable that the polymerizable polyallyl ester that is used as a binder in the practice of the invention be in partially polymerized form. Polyallyl esters are among the few types of monomeric substances whose polymerization by an addition type of polymerization reaction can be arrested while the substance is in a partially polymerized form, and then reactivated later to polymerize the substance to an iniusible, insoluble state. In the production of a composition of the invention, it is preferable that a polyallyl ester such as a diallyl ester first be partially polymerized to a soluble addition type of polymer before it is mixed with the other ingredients and then be further polymerized to form the desired type of article (e. g., molded or cast article).

Polyallyl esters may be partially polymerized by effecting the polymerization in the presence of an organic peroxide catalyst such as benzoyl peroxide, di(t-butyl) peroxide or another di(talkyl) peroxide by the procedures set forth in United States Patents Nos. 2,433,616 and 2,426,476. The amount of catalyst may range from as little as is required to bring about the reaction in a commercially feasible period of time under practical operating conditions (e. g., 0.01 per cent of the polymerizable material) to amounts as great as 10 per cent or more. (The terms per cent and parts are used. herein to mean per cent and parts by weight unless otherwise specified.) The polyi" erization can be carried out in a continu or batchwise manner, at atmospheric, superatmospheric or reduced pressures. The polmerization is generally carried out under the influence or" heat; ordinarily temperatures from about room temperature to 300 degrees C. may be used. If desired, the polymerization can be carried out in two or more different steps, using diiierent temperatures and/or diiierent catalysts.

The polymerization reaction can be stopped at any point short of completion. It is preferable that the partial polymer of a polyallyl ester that is used as a binder in the practice of the invention be a solid, soluble, fusible, poiymerizable polymer that is essentially a B stage resin. Frequently the partial polymer is somewhat brittle,

and it is then desirable to soften it with a small amount (e. g., 5 to 15 per cent) of the corresponding monomer. A lower proportion of monomer (e. g., 5 per cent) is preferred. Usually it is preferable to use the partially polymerized polyallyl ester as about a 50 per cent solution in a common non-reacting solvent such as acetone, and to mix the solution with the other ingredients such as fillers, catalysts, etc. before removing the excess of solvent and then advancing: the cure of the resin to the desired degree.

Although a polymerizaole polyallyl ester (preferably in partially polymerized form) may be the sole component of the binder in a composition of the invention, a polymerizabl unsaturated alkyd whose molecule contains a plurality of polymerizably reactive n -enedioyl groups may be used in combination with the polymerizable polyallyl ester.

A polymerizable unsaturated alkyd whose molecule contains a plurality of polymerizably reactive A -enedioyl groups is prepared by reac- 9 tion of one or more polyhydric alcohols and one or more polycarboxylic acids having in the molecule at least one polymerizably reactive n -enoyl group, having the structure e=e t Thus, the polymerizable alkyd is one having polymerizably reactive A -enoyl groups contained in dioyl radicals (connecting polyhydric alcohol residues through ester linkages) which dioyl radicals may therefore be defined as n -enedioyl radicals. The proportion of polyhydric alcohols having more than two hydroxy groups, such as lycerol or pentaerythritol, and the proportion of polycarboxylic acids having more than two carboxy groups, such as citric acid, preferably is small so that in the production of the alkyd ther may be maximum esterification of the hydroxy and carboxy groups without attainment of excessive viscosity (i. e., through crosslinking). For the purpose of the instant invention it is to be understood that the term unsaturated alkyd means an alkyd that is polymerizable into an infusible or high melting point resin; so the proportion of unsaturated components should be such that the alkyd contains an average of at least three double bonds per molecule.

Preferably, an alkyd that is used with a polyallyl ester in the binder of a composition of the invention is an ester of a glycol with a dicarboxy alkene having from four to five carbon atoms, in which the carboxy radicals are attached to adjacent carbon atoms (i. e., maleic, fumarie, itaconic, citraconic or mesaconic acid). However, as long as the A -enoyl groups are polymerizably reactive, the polycarboxylic acid is not necessarily a hydrocarbon dicarboxylic acid but may contain any radicals (e. g., chloro groups) which do not render the A enoyl groups polymerizably non-reactive. Th alkyd may be an ester of a polycarboxylic acid with any glycol, such as any polymethylene glycol in the series from ethylene glycol to decamethylene glycol, propylene glycol, any butylen glycol, any polyethylene glycol, in the series from diethylene glycol to nonaethylene glycol", dipropylene glycol, any glycerol monobasic acid monoester -(in either the alpha or beta position), such as monoformin 0r monoacetin, any monoether of glycerol with a, monohydric alcohol, such as monomethylin or monoethylin,"

or any dihydroxy alkane in which the hydroxy radicals are attached to carbon atoms that are primar or secondary or both, in the series from dihydroxy butane to dihydroxy decane. Also the polyhydric alcohol used may be one whose molecule has two or three free hydroxy groups and consists of an ether of one or two molecules of allyl or methallyl alcohol with one molecule of a polyhydroxy compound such as glycerol, pentaglycerol, pentaerythritol, butanetetrol-1,2,3,4, a

trihydroxy normal alkane having from four to five carbon atoms such as butanetriol-1,2,3, or a monoalkyl ether of pentaerythritol or butanetetrol-1,2,3,4 in which the alkyl radical has from one to four carbon atoms and has from one to two hydrogen atoms attached to the same carbon atom as the ether linkage, such as the monomethyl or monoisobutyl ether of pentaerythritol.

Part of the unsaturated dicarboxylic acid may be replaced by a saturated dicarboxylic acid, such as'any normal acid in the series from oxalic acid and malonic acid to sebacic acid, or any benzene dicarboxylic, naphthalene dicarboxylic or cyclohexane dicarboxylic acid, or diglycolic, dilaetic or resorcinol diacetic acid.

The preferred polymerizable unsaturated alkyds are the so-called linear alkyds, i. e., those which have very little cross-linking in the alkyd molecules, as evidenced by the fact that such alkyds are soluble in solvents such as acetone. Such alkyds are formed mainly by esterification of a dihydric alcohol and a dibasic acid. Of course, such alkyds are really only substantially linear since it is not possible to avoid all crosslinking, at least through the unsaturated bonds in the alkyd molecules. In fact, a linear (or substantially linear) alkyd may be obtained even though in the preparation of such alkyd a small proportion of the dihydric alcohol (e. g., less than about 5 mol per cent of the alcohol) is replaced by a polyhy-dric alcohol containing more than two alcohol radicals, such as glycerol or penta erythritol, or a small proportion of the dibasic acid (e. g., less than about 5 mol per cent or" the acid) is replaced by a polybasic acid containing more than two acid radicals, such as citric acid. The preferred linear alkyd for use in the practice of the invention is prepared by carrying out the esterifioation reaction substantially to completion (i. e., to an acid number of less than about 40) without permitting substantial (addition) polymerization to take place. Although the esterification reaction is usually carried out under an inert gas atmosphere so as to exclude oxygen, various inhibitors may be used to prevent appreciable polymerization of the alkyd during the esterification reaction.

The molecular Weight of polymerizable unsaturated alkyds for use in the practice of the invention may vary over a Wide range, depending upon the initial reacting ingredients and upon the degree of reaction obtained in the preparation of the alkyds. An alkyd used in th practice of the invention may have a molecular weight ranging from as low as about 500 to as high as about 5000, but ordinarily the molecular weights of preferred polymerizable unsaturated alkyds that may be used in the present invention are in the lower portion of the range; for example, the molecular weight of an alkyd prepared from ethylene glycol, maleic anhydride and small amounts of propylene glycol and phthalic anhy dride usually is within the range from about 70d to about 2000.

The number of repeating units in a polymeriza-ble unsaturated alkyd chain, i. e., the number of acid and alcohol residues in the chain-like molecules of the alkyd, may also vary, and alkyds having' a high molecular weight have corresponding long chain molecules. In general, in a polymerizable alkyd that may be used in the practice of the invention the number of repeating units in the alkyd chains may range from about 3 to about 25. However, in preferred alkyds used in the present invention there are usually from about 4. to about 15 units in the alkyd chains. Assuming that there is substantially no cross-linking in such polymerizable unsaturated alkyds and that equivalent quantitiesof, for example, glycol and maleic acid are employed, the number of olefinic unsaturations attached to carbon atoms in the chains of such polymerizable alkyds is, of course, merely the number of acid residues in the alkyd chain. However, if part of the maleic acid is replaced by a saturated acid in the preparation of a polyrnerizable alkyd, the number of olefinic unsaturations is lower in proportion to the amount of saturated acid employed, even though the numaboutthe same. Other properties of the unsatu- 2,cso,722

rated alkyd, such as solubility in various solvents, also may be varied by selecting various reacting ingredients varying their proportions. The infusibilil'y. hardness and inertness of the product obtained by polymerization of the alkyd may be increased by varying the initial reacting ingre ents to increase the average number of olefinic double bonds per molecule of the polymerizable alkyd.

In the preparation of the polymerizable unsaturated alkyd, any of the usual modifiers such as monobasic acids, monohydric alcohols and natural resin acids may be added. The larger the proportions oi monobasic acids and monohydric alcohols, the lower is the average number of acid and alcohol residues in the resulting alkyd molecules, and the lower is the viscosity of the alkyd. On the other hand, the more nearly equal the molecular proportions of dibasic acid and dihydric alcohol, the greater is the average number of residues in the resulting alkyd molecules, and the greater is the viscosity. The proportions of ih gredients used are those proportions that produce a polymerizable alkyd of the desired viscosity. It is desirable that the proportion of monobasic acids and monohydric alcohols be kept low enough to allow substantial growth of the chain-like mole cules during preparation of the unsaturated alkyds, since the presence of a substantial pro portion of such monobasic acids and monohydric alcohols retards the chain growth of the alkyds and produces alkyds which may not harden satisfactorily.

The eifect of the addition of a small proportion of a monohydric alcohol or a monobasic acid upon the chain growth of an alkyd is dependent to a great extent upon the degree of reaction attained before such a monofunctional acid or alcohol is added. For example, if added at the beginning of the reaction of a dibasic acid with a dihydric alcohol, each molecule of the monofunctional ingredient which reacts with a difunctional acid or alcohol stops the growth of that alkyd chain in one direction so that long chain molecules of the alkyd are difiicult to obtain under such conditions. However, if added when the reaction or dibasic acid and dihydric alcohol is almost complete so that fairly long chains have already been built up, the nionoiunctional ingredient merely esterifles those end groups present in the existing alkyd chains and, therefore, only a small amount may be incorporated in the alkyd without having any deleterious eilect upon the final product.

The proportion oi monohydric alcohol or monobasic acid used should never be above about 10 mol per cent of the or alcohol content. Ordinarily the proportion of monohydric alcohol or monobasic acid that may be incorporated in polymerizable unsaturated alkyds for use in molding compositions of the invention is not more than about mol cent or the alcohol or acid content, although alkyds used in casting compositions occasionally may contain a slightly higher proportion of monofunctional ingredients. However, polyrnerizable unsaturated alkyds which may be used in the practice of the invention usually contain not more than about 2 mol per cent of monofunctional acid or alcohol in order that such.

alkyds may be readily polymerized into infusible or high melting point resins.

The point to which the reaction of the ingredients is carried in the preparation or" the polymerizable alkyd is simply that point at which the product has the desired consistency. The consistency or viscosity of the alkyd (prepared by reaction under conditions which prevent any appreciable addition polymerization) varies directly with the average number of acid and alcohol residues in the molecule.

If desired, the reaction may be expedited by use of an acid substance as a catalyst. Any organic acid, inorganic acid or acid salt that is soluble in the reaction mixture may be employed as a catalyst, but it is desirable that any acid substance used be readily volatile or be of such a character that it has no deleterious effect in the final product. The amount or" said catalyst employed is simply that amount which accelerates the esterification to the desired degree.

The reaction is carried out at a temperature high enough and for a time long enough to secure the desired consistency. An elevated temperature preferably is employed to expel ite the reaction, but during the preparation of the alkyd. the temperature should not be so high nor the time of reaction so long as to cause substantial polymerization. There is less danger of premature polymerization if an inhibiting agent is added before the esterification is carried out.

Whenever added, an inhibiting agent is used in the proportion required to give the desired degree of inhibiting effect. It may be necessary to use different inhibitors in widely different prc portions in order to secure the same inhibiting effect.

Any desired anti-oxidant such as hydroquinone, pyrogallol, tannic acid or any aromatic amine, such as aniline or phenylene diamine may be employed as an inhibitor.

The preparation of the unsaturated alkyd prcf erably is carried out in an atmosphere of an inert gas such as carbon dioxide, nitrogen or the like, in order to prevent cross-linking through addition polymerization as well as to prevent darkening or to make it possible. to obtain a pale or colorless product. Bubbling the inert gas through the reacting ingredients is advantageous in that the as serves the added functions of agitation and of expediting the removal of water formed by the reaction. Exclusion of oxygen is desirable not only because oxygen causes discoloration, but also because it tends to produce premature polymerization at the elevated temperatures used.

The acid number of the product depends upon the degree of reaction and the proportions of acid and alcohol used for the reaction. With eouimolecular proportions of dibasic acid and dihydric alcohol, the reaction may be carried to an acid number of about 20. The use of an acid catalyst may make it possible to attain a lower acid number without substantial polymerization.

A polymerizable alkyd may be prepared by the following procedure:

A three-necked flask is employed in which 5.4 mols of maleic anhydride and 5.4 mole of diethylene glycol are mixed together. The flask is then fitted with a thermometer, a tube leading to a condenser and an inlet tube through which is introduced a. moderate stream of carbon dioxide, and is lowered into an oil bath at a temperature of 210 C. During the subsequent reaction the distillate rnay be analyzed, and a sutficient amount of the ingredient lost in excess may be added to the flask from time to time to maintain the initial proportions of reacting ingredients. If the only addition is a sufficient amount of the ingredient lost in excess to maintain the initial proportions, the rate of removal of unreacted ingredients gradually decreases and having an acid number of 18.

substantially no unreacted ingredients may be left in the composition at the end of the reaction. After 8 hours at such temperature, an alkyd is obtained in the form of a stifi liquid If ethylene glycol were substituted for the diethylene glycol in the foregoing procedure, it would be diiiicult to reduce the acid number below 40 without causing polymerization, and the product would be a very thick gum.

Alternatively, this first procedure, as described in the foregoing paragraph, may be employed except that 1.5 instead of 5.4 mols of maleic anhydride and 1.5 instead of 5.4 mols of diethylene glycol are used together with an amount of hydroquinone equal to 0.2 per cent of the weight of the reacting ingredients; and reaction is continued for 6%; hours. The resulting alkyd is a moderately stiff liquid having an acid num ber of 11.

A further procedure that may be used is the same as the first procedure except that 2 instead of 5.4 mols of maleic anhydride and 2.1 instead of 5.4 mols of diethylene glycol are used; and the reaction is carried out for 4 hours to produce a stiff liquid having an acid number of 14.

Another type of polymerizable alkyd may be prepared by a procedure that is the same as the first procedure except that 3 instead of 5.4 mols of maleic anhydride and 33 instead of 5.4 mols of diethylene glycol are used together with an amount of hydroquinone equal to 0.09 per cent of the weight of the reacting ingredients and an amount of p-tolune sulfonic acid equal to 0.18 per cent of the Weight of the reacting ingredients; and the reaction is carried out for four hours at 200 C. to produce a stiff liquid having an acid number of 10.6.

As a further alternative, the first procedure may be employed except that the amount of maleic anhydride employed is 6 instead of 5.4 mols; the diethylene glycol is replaced by 6 mols of ethylene glycol; a slower stream of carbon dioxide is used; and the ingredients are kept in an oil bath at 220 C. for hours. The resulting alkyd is a very thick gum having an acid number of 53.

A polymerizable alkyd may also be prepared by a procedure that is the same as in the preceding paragraph except that the maleic anhydride is replaced by 5 moles of fumaric acid; the ethylene glycol is replaced by 5 moles of diethylene glycol; and the reaction is continued for 8 /4 hours. The resulting alkyd is a stifi liquid having an acid number of 23. If in the foregoing procedure the diethylene glycol were replaced by an equimolecular proportion of ethylene glycol and half of the fumaric acid were replaced by an e uimolecular proportion of phthalic anhydride, the product would be a hard "brittle solid. The substitution of fumaric acid the same, the resulting alkyd tends to be more viscous and greater care is necessary in order to prevent premature polymerization.

As further variation, the first procedure may be used except that the maleic anhydride is replaced by 1.5 mols of fumaric acid; the amount v of diethylene glycol employed is 1.5 instead of 5.4 mols; and the temperature is varied between 14 200 and 220 C. After the reaction has been continued for 2 hours, the acid number is '73. After 6 hours, the product is a stiff liquid having an acid number of 41.

A polymerizable alkyd may also be prepared by a procedure that is the same as that of the preceding paraghaph except that p-toluene sulfonic acid (1.5 grams) is added to the initial ingredients; and reaction for only 2%.; hours instead of 6 hours is required to produce a stiff liquid having an acid number of 41.

A procedure that may also be used is the same as that of the next to the last paragraph except that the furnaric acid is replaced by 3.3 mol of maleic anhydride; the amount of diethylene glycol used is 3.0 instead of 1.5 mols; 1.5 grams of p-toluene sulfonic acid and 1.3 grams of hydroquinone are added to the initial ingredients; and the reaction is carried out for 3 hours to produce a limpid liquid having an acid number of 26.-

A polymerizable alkyd may be prepared by a procedure that is the same as the next to the last paragraph except that 3 instead of 1.5 mols of fuma-ric acid and 3.3 instead of 1.5 mols of di- 7 ethylene glycol are used; and the reaction is carried out for 3 hours at temperatures ranging from 200-210 C. to produce a stiff liquid having an acid number of 12.

A further procedure that may be used is the same as that of the next to the last paragraph except that the hydroquinone is omitted; and reaction for 5 hours is required to produce a stiff liquid having an acid number of 28.

Another procedure that may be used is the same as the procedure of the next to the last paragraph except that the weight of p-toluene sulfonic acid is equal to 0.18 per cent of the weight of the reacting ingredients; an amount of hydroquinone equal to 0.09 per cent of the Weight of the reacting ingredients is added at the start of the reaction; and reaction is carried out at 200 C. for 5 hours to produce a stiff liquid which has an acid number of 10.1.

A molded polyallyl ester composition of the invention, like a molded unsaturated alkyd composition, has excellent dimensional stability characteristics since no volatile products are evolved during the curing reaction. Furthermore, a molded polyallyl ester composition of the invention, like a molded unsaturated alkyd composition, has good electrical characteristics, including arc resistance. A molded polyallyl ester composition of the invention has greater resistance to hydrolysis (and thus better retention of electrical properties under high humidity conditions), in general, than a molded unsaturated alkyd composition. Polyallyl ester molding compositions,

in general, also possess greater stability than unsaturated alkyd molding compositions. On the other hand, polyallyl ester molding compositions do not cure as rapidly and, when molded, are slightly weaker in mechanical strength than unsaturated alkyd molding compositions. Thus, upon replacing a portion of the polymerizable polyallyl ester in a composition of the invention with a polymeriztble unsaturated alkyd, the prop erties of the composition will be intermediate between those of an unsaturated alkyd compoition and those of a polyallyl ester composition. In general, when the binder in a composition of the invention comprises a polymerizable unsaturated alkyd in addition to the polymerizable p-olyallylester, the proportion of the unsaturated alkyd may be as high as 35 per cent of the binder,

the poiymerizable polyallyl ester being not less than 65 per cent of the binder.

Filler The filler in a composition embodying the invention comprises kaolin that has been dehydrated by calcining at 690-1200 degrees C.

Dehydrated clays are well known materials produced from ordinary clays by a calcining operation at a temperature sufficient to drive off the chemically combined water and to effect the combustion of organic matter without fusing the clays. Dehydrated kaolin for use in the practice of the present invention may be prepared by heating ordinary kaolin (i. e., Georgia clay) in a rotary kiln at a temperature suillcient to drive off the chemically combined water (i. e., at least about 600 C.) but below the temperature which would produce sintering of the kaolin (i. e., about 1200 C.). alkali or alkaline earth metal or of an ainphoteric metal (e. g., sodium chloride, potassium chloride, sodium bromide, sodium nitrate. sodium sulfite, sodium hydroxide, calcium chloride, magnesium chloride, aluminum chloride, zinc chloride, or mixtures thereof) may be incorporated in the kaolin before heating. For example, dehydrated kaolin may be prepared by pulverizing ordinary kaolin (603 pounds) and sodium chloride (18 pounds) and heating the mixture in a batch-type rotary kiln for about five hours at a temperature of about 785 C. to produce a loss in weight of about 1%.8 per cent or" the mixture. If such a procedure is carried out at temperatures ranging from 900 to 955 C. the loss of weight of the mixture is about 15.0 per cent.

It is preferable that dehydrated kaolin be the sole filler in a composition of the invention. However, the improvements imparted by dehydrated kaolin are so great that a combination of dehydrated kaolin with other fillers such as asbestos, resin-coated asbestos and resin-treated cellulose may be used to obtain compositions which can be molded into articles having excellent resistance to hydrolysis and good strength characteristics. (Fillers such as asbestos and cellulose, as hereinbefore demonstrated, cannot be used alone without a serious impairment of the water resistance and strength of articles molded from the coil positions.)

Although the term asbestos in commercial use has come to mean only the prevalent Canadian asbestos, i. e., chrysotile (as the mineral occurring naturally and as the fibers resulting from processing the mineral), strictly speaking asbestos is a generic term applicable to silicate minerals having a fibrous structure. The term asbestos is used hereinafter in its more strict meaning, i. e., to include not only chrysotile fibers but also other silicate mineral fibers, which may be used. as fillers in combination with dehydrated kaolin in compositions of the invention.

If desired, a salt or hydroxide of an um) and trivalent metals (e. g., aluminum or ferric iron). Examples of such pyroboles include:

mountain leather and The pyroboles are further classified into two distinct classes or families, viz. amphiboles and. pyrorenes. According to J. W. Mellor in Inorganic and Theoretical Chemistry (Longmans, Green and (30., 1925) volume VI, pages 390 and 39 diopside and wollastonite are pyroxenes; and anthopliyllite, tremolite and actinolite are amphiboles. Fibrous pyroboles are available commercially in the form of the crude ore from the mine and in the form of fibers obtained by milling the ore (e. in a crusher) and then separating the fibers from the rock residue (e. g., by suction). Ordinarily, the fibers commercially available must be purified further for use as fillers, since such fibers usually contain a substantial amount (3;. mineral impurities which affect deletericusly many of the properties of the hardened compositions. The necessity and extent of purification are dete "mined by the nature of the impurities, effect on the mechanical strength of molded articles and their damaging effect on the mold itself. Pyrobole fibers sufficiently purified for use as a filler may be obtained by carrying out a simple flotation process, e. g., by introducing water continuously into the bottom of a vessel equipped with an overflow and containing the pyrobole hers, so that the impurities remain at the bottom of the vessel and the purified fibers iioat out with the overflowing water. If extreme purity of the fibers is required, tremolite fibers are preferred, since tremolite occurs naturally in a very pure state and often requires little or no further purification.

Fibrous pyroboles occur in various fiber lengths ranging up to as much as 7 inches, but the fiber lengths are reduced substantially in the ordinary milling process. No particular fiber length is reuired pyrobole fibers used as fillers, and the selection of the fiber length depends upon the desired properties and the intended use of the final product. For example, if the pyrobole fibers are to be used as a filler in a molding compound, the fibers are ground down to the size of ordinary fibrous fillers for use in such compounds, 1. e.,

1 the fiber lengths of groups No. 6 and N0. '7 of the Canadian asbestos classification, at which the fibers appear to the naked eye to be similar in form to sawdust.

In general, a combination of dehydrated kaolin with chrysotiie asbestos is preferred when a mixture of dehydrated kaolin and asbestos is employed a filler in the practice of the invention.

If desired, the chrysotile asbestos may be heat treated as described in British Patent No. 559,183.

A mixture of dehydrated kaolin and resintreated cellulose is also a desirable filler combination in a composition of the invention.

The term resin-treated cellulose is used here- 1 7 .c in to include any form of cellulose filler (for example, alpha cellulose, shredded paper, chopped cloth (e. g., canvas);cottonfloclr, cotton linters, purified wood fibers in finely ground forms or in felted-fiber forms, cotton cord or regenerated cellulose) which has been impregnated with a thermosetting heterocyclic polyamine-formaldehyde reaction product converted to its infusible state on the cellulose. The heterocyclic polyamine that is reacted with formaldehyde to form a thermosetting reaction product to be used to coat cellulose is a substance whose molecule has a plurality of NH2 groups each connectedto a carbon atom contained in a heterocyclic ring, the ring consisting of from five to six carbon and nitrogen atoms of which not more than three are nitrogen atoms, and such carbon atom being connected by a double bond to an intracyclic nitrogen atom.

When the heterocyclic ring comprises a triazole ring, the heterocyclic polyamine may be, e. g., guanazole I I I MG N=c When the heterocyclic ring in the heterocyclic polyamine comprises a diazine ring, the heterocyclic polyamine maybe, e. g a pyrimidine such as 2,4-diamino-6-hydroxy pyrimidine,

2 HO-C N When the heterocyclic ring in the polyamine comprises a triazine ring, the heterocyclic polyamine may be a substance whose molecule contains from one to three triazine rings, and has no functional groups attached to a triazine ring other than the amino groups (such as an amino triazine). The term functional group as used herein means any radical in a molecule of such a substance which may enter into undesirable side reactions that interfere with the reaction of formaldehyde with-the amino triazine (e. g., an OH group attached to a triazine ring may react with formaldehyde during the production of a thermosetting amino triazine-formaldehyde condensation product). A heterocyclic polyamine that has one triazine ring in its molecule may be (1) a triamino t'riazine e. g., melamine,

wherein R is a hydrogen atom, a saturated monovalent aliphatichydrocarbon radical having from 1 to 18 carbon atoms, an aromatic hydrocarbon radical containing 1 benzene nucleus or containing 2 condensed benzene nuclei, a saturated or unsaturated cycloaliphatic hydrocarbon radical, or any of the foregoing radicals containing substituents such as aliphatic, cycloaliphatic, aromatic, alkoxy, aryloxy and acyl radicals. Thus, the monoguanamines used may have varying structures and may be of complex structure so long as they do not contain groups which interfere with the condensation reaction of formaldehyde with the guanamine.

Such monoguanamines include:

formoguanamine NH: N-C

acetoguanamine I NH:

propioguanamine H|C- UHF-0% N=C v I NH:

butyroguanamine phenylacetoguanaminc delta-cyano-valeroguanamine wherein R is a divalent hydrocarbon radical in which the shortest connection between the free valences is not more than eighteen carbon atoms in series and which contains no substituents or contains substituents such as aliphatic, cycloaliphatic, aromatic, alkoxy, aryloxy and acyl radicals, or may be a compound having said general formula that is substituted on not more than two exocyclic nitrogen atoms, the substituents consisting of (a) not more than two monova-lent aliphatic hydrocarbon radicals on each substituted nitrogen atom, each having not more than four carbon atoms, each having at least one hydrogen atom attached to the same carbon atom as the free valence, and each having not more than one unsaturation, any such unsaturation being an olefinic unsaturation in the beta-gamma position, (b) not more than one monovalent radical of the benzene series on each substituted nitrogen atom, having not more than eight carbon atoms in which the free valence is connected to the nucleus, and (c) not more than one monoalkoxy phenyl radical on each substituted nitrogen atom, having not more than eight carbon atoms. Thus the diguanamines used may have varying structures and may be of complex structure so long as they do not contain groups which interfere with the condensation reaction of formaldehyde with the ,diguanamine. Such diguanae mines include sebacoguanamine adipoguanamine bis-(4,fi-diamino-2-triazinyl-ethyl) fluorene gamma-isopropenyl-gamma-acetyl pimelcguanamine CHa- O ghthaloguanamine D,D'-bis-ZA-diamino-G-triazinyl diphenyl :mesozzaa 1,2-bls-z4-dlamino-dgtrloslnyl naphthalene gamma-phenyl-pimeloguanamine; m

, A'thermosettin'g heterocyclic' polyamine-form-' aldehyde reaction productfmay 'befobtained Y by reacting a .heterocycli'c po1yamme; as *hereihbe fore'defined (or a mixture of such amines)", either' with formaldehyde or with" a" polymer thereof, such as paraformaldehydei Whenused for'this reaction,'paraformaldehyde is considered to split up so'that the substance actually tak: ing part in the reaction is formaldehydefiThe heterocyclic polyamine may be reacted with a solution of formaldehyde inwaterfi'n' an'organic solvent such as an alcohol, or ina liquid containing' both water an'd'an organic solvent.

'A water solution is'usually 'preferredk fThe reaction may" be performed 1 in "an autoclave, if desired, to secure a reaction temperature above the'boilingpoint of the "solvent; "Ordinarily; the heterocyclic polyamine is added aqueous formaldehyde solu'tion having a pH of about 4, or to such a solutionfwhich hasben made less' acid,- or neutral or alkaline," preferably at a pH between 6 and 8, by-addition of any desired base, such as sodium hydroxide, ammonium hydroxide, borax or triethanol'amine'; I

'In' general; the proportion of formaldehyde actually reacting may range from one half to a maximum of two'molecules for each aminogroup; An excess of formaldehyde above this'maximinn may be used for the reaction if desired, although an uncombinable excess of one of thereactants usually is not desirable in the final product. Because of the complexity of the molecules of the reaction products that are produced, the

proportion of formaldehyde actually reacting may vary freely between the limitsstated, The

preferred proportions'vary, of course, with specific substance that is reacted with formaldc For example, when the substance -is hyde.

to acor'hr'nercial' melamine; lithe preferred proportidns are about sebacoguanamine;

The reaction proceeds at normal temperatures, but heating ordinarily is desirable to shorten the time 'of'reaction,or, in some cases, to dissolve the'substance to be reacted with formaldehyde. The desired resin solution ordinarily is obtained bycarrying the reaction only to its earliest stage, for example, the'stage at which the reacting ingredients havejustdissolved to'form a solution, or fora few additional minutes thereafter. I .When the reactio'nbetween formaldehyde and a heterocyclic polyamine is substantially complete, the solution is diluted with water or any suitable solventso that the weight of the diluted solution-is from two'to three times the weight of the cellulose to be'treated-j (The weight of the-cellulose is always taken as its bonedry weight. -The cellulose'employ-ed need notb e bone dry, of course, so long as its water content isaccounted for in calculating its weight) The dilution'should be made carefully so that the resin does not precipitate'as-the water is added; Ita-is desirable that the pH 'of the resin solution be adjusted (e. g.', with dilute lactic acid) so that it is onthe'slightly acid side, since the resin cures to its infusible state son the filler more rapidly in a slightly acid condition. (The preferred-pI-I varies: in accordance with the particular heterocyclic' polyamine-formaldehyde reaction product solution employed. Melamineformaldehyde reaction product solutions are preferably used at a pH betwe'enfi and 6;) "When the reaction product has thoroughly impregnated the-cellulose filler, it is essential that -the-material be thoroughly driedand that the resinous reaction product'be cured'on the filler to the infusible state. Although the slightlyacid 5 pH of'the impregnating solution aids the cure initiallyyseveral hours of heating may be necessary at an elevated temperature to completely: deaden the resinous substance. (Melamine-formaldehyde resins derived from solutions having a pH-between 5 and 6 usually cure-in about three hours at temperaturesranging from-200 to 225 F.) The-completeness of cure'may'bechecked from time to time during the curing operation by'boiling" 'a's'ample of the treated filler-in water. If the cure isstill incomplete, -a*cloudy solution will result because ofdissolved resinous reaction product.- On the other hand; if the solution is clear, complete cu're is-indicated:

;--T-he-- proportion of a-heterocyclic polyamine- '7 formaldehydereaction product solution used to impregnate a cellulose filler should be such that from 2.5 to 40 per cent of thefinaltreated'dryfiller consists of the heterocyclicpolyamine- 4 formaldehyde reaction product in its infusible state It is preferred that the proportion of the reaction product solution be such that from about 14 to about 25 per cent of the final treated filler consists of the reaction product in its infusible I state;

Any of the asbestosfillers hereinbeforede- 01: scribed, before being'used in combination with dehydrated kaolin, may be coated with a thermosetting'reaction product of formaldehyde and a heterocyclic polyamine. In the preparation of such a resin-coated filler, the heterocyclic polyamine-formaldehyde reaction product solution is diluted with water or any suitable solvent so that the volume of the resin solution is such that it may be used to deposit only a very small amount of the resin as a coating on the filler, the extent of the dilution varying, of course, with the procedure employed for applying the resin'to the filler, as is hereinafter further discussed. The dilution should be made carefully so that the resin does not precipitate as the water is added. It is desirable that before dilution the pH of the resin solution be adjusted (e. g., with dilute lactic acid) so that it is on the slightly acid side, to prevent precipitation of methylols upon dilution and to promote condensation of the resin.

When the reaction product has thoroughly coated the asbestos filler, it is desirable that the material be subjected to strong heating, since the heterocyclic polyamine-formaldehyde reaction product should be in at least a relatively advanced state of condensation. It is ordinarily desirable that the reaction product be in an infusible state, but at least the resin on the filler should be sumciently condensed that neither water nor formaldehyde will be liberated during further processing operations in the preparation of a molding composition. Although the slightly acid pH of the coating solution may aid the cure intially, several hours of heating may be necessary at an elevated temperature to bring the resinous substance to a sumciently advanced state of condensation (or to an infusible state in accordance with the preferred procedure). 'Any desired method may be used to coat the filler with the resin, so long as care is taken to avoid breakdown or wadding of the filler fibers. Of course, the preferred procedures are those which result-in the least change in the physical characteristics of the filler. For example, the filler may be stirred into a highly dilute solution of the desired resin to form a slurry that can be readily atomized for spray drying or can be vacuum drum-dried. Alternatively, a dilute resin solution may be absorbed on the filler in a mixer and the resulting mass dried on trays at an elevated temperature (e. g., about 160 degrees F.). If desired, the dry product may be screened into several fractions to remove any fibers which may have become Wadded or balled up during the coating process. However, such agglomerates ordinarily require hammer milling in order to break them up, and such a procedure may result in a considerable destruction of the fibers. A desirable procedure for coating an asbestos filler Which produces very little harmful effect upon the physical characteristics of the fibers consists in stirring the filler into a dilute solution of the desired resin, allowing the slurry to stand for a short period of time (e. g., about fifteen minutes) and then filtering the slurry. The filter cake so obtained may then be dried and screened, and the screened fibers further dried. Ordinarily, it is preferred that approximately 2 to 25 per cent of the final treated dry filler consist of the heterocyclic polyamine-forinaldehyde reac tion product (preferably in its infusible state), and it is most desirable that the proportion of the reaction product solution be such that from about 5 to about per cent of the final coated filler consist of the reaction product.

r 24 Catalysts As hereinbefore stated, it is preferable that the polyallyl ester which is used as a binder in a composition of the invention be in partially polymerized form. Usually a solution of the partially polymerized polyallyl ester in acetone or another solvent is used, and the solvent is removed during the production of a molding composition. If a peroxide catalyst is added to the solution before the solvent is removed, the partially polymerized resin can be further polymerized by heating to the desired degree of cure.

The preferred catalyst for use in the production of a composition of the invention is t-butyl perbenzoate, but any other organic peroxide (not containing polymerization inhibiting radicals), such as succinyl peroxide, benzoyl peroxide, di-tbutyl perphthalate, acetyl peroxide, paracetic acid, perbenzoic acid, toluyl peroxide, p-bromobenzoyl peroxide, anizoyl peroxide, chloroacetyl peroxide, acetyl benzoyl peroxide, diacetyl peroxide and furoyl peroxide; or any organic ozonide (not containing polymerization-inhibiting radicals), such as di-isopropylene ozonide or diisobutylene ozonide, or a mixture of such substances may be used as the curing catalyst.

Production of polymerizable composition The polymerizable compositions of the invention include molding, casting and adhesive compositions.

In the production of a molding composition of the invention, it is preferable that a polymerizable polyallyl ester such as a diallyl ester first be partially polymerized to a soluble addition-type polymer, as hereinbefore described. A solution of this polymer in acetone or other solvent is then mixed with the filler, catalyst and other ingredients of the composition in a dough or sigma-bladed mixer. The solvent is removed by drying, e. g., at temperatures around 140 degrees F. for several hours, or by venting of the vapors followedby passage of Warm air over the mixture for about onehalf hour. The resin cure is then advanced to the point where the composition ofiers sufilcient resistance to flow in the mold to have satisfactory molding properties, e. g., by mixing for ten minutes on differential rolls or for a few minutes on a heated roll mill. Care should be taken not to advance the polymerization too far during the mixing operation, or the product may be stifi or even unmoldable.

The proportion of dehydrated kaolin used as a filler in a polymerizable polyallyl ester composition embodying the invention may range from the minimum amount capable of appreciably improving the physical properties of the hardened product (i. e., about 5 per cent of the composition) to the maximum proportion which may be held together or bound satisfactorily by the polyallyl ester binder (i. e., about per cent of the composition) for the dehydrated kaolin filler in a molding composition of the invention is from about 55 percent to about 70 per cent of the composition, and the optimum results are obtained in the upper portion of such range.

A resin-treated cellulose filler when used in combination with dehydrated kaolin in a composition of the invention may be in a proportion as high as 1 part for every 2 parts of dehydrated kaolin, the total filler content being within the range specified for dehydrated kaolin as the sole filler.

In general, the preferred range An asbestos filler (i. e., a chrysotile, a heattreated chrysotile, a fibrous silicate, or a resincoated chrysotile or fibrous silicate filler) when used in combination with dehydrated kaolin in a composition of the invention may be in a proportion that is as high as 1 part for each part of dehydrated kaolin, the total filler content being within the range specified for dehydrated kaolin as the sole filler.

The proportion of curing catalyst used in the practice of the invention is simply the proportion that causes the composition to polymerize at the desired rate, and as the term catalyst implies, such proportion is the usual catalytic amount, i. e., ranging from about 0.5 per cent to about 1 or 2 per cent of the composition. The preferred proportion of curing catalyst varies with the difierent catalysts, and the amount of any particular curing catalyst required to produce a given rate of hardening may vary also with variations in the nature of the polymerizable composition.

When the present method is carried out in the production of a molding composition or a casting composition, plasticizers, lubricants, pigments and other coloring matter may be incorporated if desired.

The following example illustrates the practice of the invention: 7

Example A composition of the invention is prepared as follows: A solution of a partially polymerized polyallyl ester (2590 grams consisting of 50 per cent of acetone solvent and 50 per cent of diallyl phthalate of which 95 per cent is in the form of a soft, solid fusible polymer melting in the range from 210 to 220 degrees F.) is mixed in a Hobart dough mixer with a catalyst (51.8 grams of t-butyl perbenzoate), dehydrated kaolin (1330 grams), anthophyllite fibers (8'75 grams) and zinc stearate ('70 grams). The mixing is continued until a homogeneous material is obtained, which material is then dried at 140 degrees F. for three hours to remove the excess of acetone solvent. The material is then milled on olifierential rolls for about ten minutes. The resulting sheet is cooled and then granulated in a high speed cutter. The granular composition, hereinafter referred to as composition B, is molded and tested by the procedures hereinbefore described, the results being tabulated in Table 4. below.

For the sake of comparison, the results obtained on articles molded from two control compositions are also included in Table 4. Control (a) is prepared by the procedure described for composition B except that the filler consists only of anthophyllite fibers (2400 grams) and the proportions of the other ingredients are as follows: 3200 grams of the solution of partially polymerized diallyl phthalate; 64 gramsof t-butyl perbenzoate; and 80 grams of zinc stearate.

Control (1)) is prepared by the procedure described for composition B except that the filler consists of anthophyllite fibers (1710 grams) and zinc oxide (150 grams) and the proportions of 26 the other ingredients are as follows: 2280 grams of the solution of partially polymerized diallyl phthalate; 45.6 grams of t-butyl perbenzoate; and grams of zinc stearate.

TABLE 4 Composition control control Boiling water, abs, 1 hr Cold water, abs, 24 hrs Cold water, abs., 48 hrs. Cold water, abs., 7 days Dielectric constant, 60 cycles-- Dielectric constant, 10 cycles Power factor, 60 cycles Power factor, 10 cycles Insulation resistance (meg 7 days 14 days 21 days 28 days Flexural (p. s. i. Compressive (p. s. i.)..

pr s?? mm 80 Ho 0000 P w w mm HOD sess saws...

f innl Having described the invention, I claim:

1. A material which upon polymerization has improved water resistance and electrical properties, comprising (a), as a binder, a polymerizable polyallyl ester, and (b), as a filler, kaolin that has been dehydrated by calcining at 600-1200 C., at least per cent of the total binder in said composition consisting of a polymerizable poly allyl ester binder, and at least 50 per cent of the total filler in said composition consisting of (b).

2. A material as claimed in claim 1 wherein the polyallyl ester is partially polymerized.

3. A material as claimed in claim 2 wherein the polyallyl ester is diallyl phthalate.

4. A material as claimed in claim 2 that comprises chrysotile asbestos.

5. A material as claimed in claim 1 that comprises asbestos.

6. A material as claimed in claim 1 that comprises a cellulose filler coated with an infusible reaction product of formaldehyde and a substance whose molecule has a plurality of NH2 groups each connected to a carbon atom contained in a heterocyclic ring, the ring consisting of from five to six carbon and nitrogen atoms of which not more than three are nitrogen atoms, and said carbon atom being connected by a double bond to an intracyclic nitrogen atom, said coated cellulose filler constituting not more than onethird of the total filler in said composition.

'7. A material as claimed in claim 6 wherein the substance is melamine.

References Cited in the file Of this patent UNITED STATES PATENTS Schule July 29, 1952 Bearing et a1. Dec. 23, 1952 Cordier Dec. 23, 1952 Sussenbach June 6, 1950 I 

1. A MATERIAL WHICH UPON POLYMERIZATION HAS IMPROVED WATER RESISTANCE AND ELECTRICAL PROPERTIES, COMPRISING (A), AS A BINDER, A POLYMERIZABLE POLYALLYL ESTER, AND (B), AS A FILLER, KAOLIN THAT HAS BEEN DEHYDRATED BY CALCINING AT 600-1200* C., AT LEAST 65 PER CENT OF THE TOTAL BINDER IN SAID COMPOSITION CONSISTING OF A POLYMERIZABLE POLY ALLYL ESTER BINDER, AND AT LEAST 50 PER CENT OF THE TOTAL FILLER IN SAID COMPOSITION CONSISTING OF (B). 